1,2,3,3,5,6-Hexamethyl-bicyclo[2.2.2]-oct-5-en-2-ol, process for producing same, intermediates useful in said process and organoleptic uses of same

ABSTRACT

Described is 1,2,3,3,5,6-hexamethyl-bicyclo[2.2.2]oct-5-en-2-ol as a mixture of isomers and in its isomeric forms and the uses thereof in augmenting or enhancing the aroma of perfume compositions, perfumed articles, and colognes.

This is a divisional of application Ser. No. 535,800, filed Sept. 26,1983, which in turn, is a divisional of application for U.S. LettersPatent, Ser. No. 371,930 filed on Apr. 26, 1982 now U.S. Pat. No.4,434,085 issued Feb. 28, 1984.

BACKGROUND OF THE INVENTION

Our invention describes1,2,3,3,5,6-hexamethyl-bicyclo[2.2.2]oct-5-en-2-ol and isomers thereofdefined according to the structures: ##STR1## and uses thereof inaugmenting or enhancing the aroma of perfume compositions, colognes andperfumed articles.

Bicyclo[2.2.2]octane derivatives are shown to be useful as fragrances inU.S. Pat. Nos. 3,929,676, 3,914,322 and 3,967,629 all of which areincorporated herein by reference. Thus, these patents disclosegenerically compounds defined according to the structure: ##STR2##wherein one of R₂, R₃, R₄ and R₅ can be hydroxyl and the other of R₂,R₃, R₄ and R₅ are methyl or hydrogen and wherein R₁, R₆, R₇, R₈, R₉ andR₁₀ can be methyl or hydrogen. It is indicated also in these patentsthat these compounds can be useful in augmenting or enhancing perfumecompositions and can be used to contribute various woody, camphoraceous,patchouli or floral fragrances. Specifically, these patents discloseperfume uses of the compounds defined according to the structures:##STR3##

However, the specific compounds of the instant invention definedaccording to the structures: ##STR4## although covered by the genericformula: ##STR5## have unexpected, unobvious and advantageous propertiesinsofar as their uses in augmenting or enhancing the aroma of perfumes,perfume compositions and colognes are concerned.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the reaction product of Example I havingthe structure: ##STR6## (conditions: SE-30 column programmed from 120°C. to 210° C. at 8° C. per minute).

FIG. 2 is the mass spectrum for the peak indicated by reference numeral"101" of FIG. 1 for the compound having structure: ##STR7##

FIG. 3 is the infra-red spectrum for the compound of peak 101 of FIG. 1having the structure: ##STR8##

FIG. 4 is the NMR spectrum (Solvent: CFCl₃ ; Field strength 100 MHz) forthe peak indicated by reference numeral "101" of FIG. 1 for the compoundhaving the structure: ##STR9##

FIG. 5 is the GLC profile for the reaction product of Example IIcontaining the compound defined according to the structure: ##STR10##

FIG. 6 is the mass spectrum for the compound of peak 501 of FIG. 5having the structure: ##STR11##

FIG. 7 is the NMR spectrum for the compound of peak 501 of FIG. 5 havingthe structure: ##STR12## (Solvent: CFCl₃ ; Field strength 100 MHz).

FIG. 8 is the infra-red spectrum for the compound of peak 501 of FIG. 5having the structure: ##STR13##

FIG. 9 is the GLC profile for fraction 2 of the distillation product ofthe reaction product of Example III containing the compounds definedaccording to the structures: ##STR14##

FIG. 10 is the mass spectrum for the peak indicated by reference numeral"901" of FIG. 9 for one of the compounds produced according to ExampleIII having one of the structures: ##STR15##

FIG. 11 is the infra-red spectrum for the compound of peak 901 of FIG. 9having one of the structures: ##STR16##

FIG. 12 is the NMR spectrum for the compound of peak 901 of FIG. 9produced according to Example III containing one of the compounds havingthe structures: ##STR17## (Solvent: CFCl₃ ; Field strength 100 MHz).

FIG. 13 is the mass spectrum for the peak indicated by reference numeral"902" of FIG. 9 for one of the compounds having the structures:##STR18## produced according to Example III.

FIG. 14 is the infra-red spectrum for the peak indicated by referencenumeral "902" of FIG. 9 for one of the compounds produced according toExample III having one of the structures: ##STR19##

FIG. 15 is the NMR spectrum for the peak indicated by reference numeral"902" of FIG. 9 for one of the compounds produced according to ExampleIII having one of the structures: ##STR20##

FIG. 16 is the GLC profile for the reaction product of Example IVcontaining the compound having the structure: ##STR21##

FIG. 17 is the mass spectrum for the peak indicated by reference numeral"162" of FIG. 16 for the compound produced according to Example IVhaving the structure: ##STR22##

FIG. 18 is the infra-red spectrum for the peak indicated by referencenumeral "162" of FIG. 16 for the compound produced according to ExampleIV having the structure: ##STR23##

FIG. 19 is the NMR spectrum for the compound of the peak indicated byreference numeral "162" of FIG. 16 for the compound produced accordingto Example IV having the structure: ##STR24##

FIG. 20 is the GLC profile for the reaction product of Example Vcontaining the compound defined according to the structure: ##STR25##

FIG. 21 is the infra-red spectrum for the compound of peak 201 of FIG.20 which is for the compound produced according to Example V having thestructure: ##STR26##

FIG. 22 is the NMR spectrum for the compound of the peak indicated byreference numeral "201" of FIG. 20, the compound produced according toExample V having the structure: ##STR27## (Solvent: CFCl₃ ; Fieldstrength 100 MHz).

FIG. 23 is the mass spectrum for the compound of the peak indicated byreference numeral "201" of FIG. 20, the compound produced according toExample V having the structure: ##STR28##

FIG. 24 is the GLC profile for the reaction product of Example VIcontaining the compound defined according to the structure: ##STR29##

FIG. 25 is the GLC profile for the reaction product of Example XXcontaining the isomers defined according to the structures: ##STR30##wherein the ratio of isomers is 1:3.

FIG. 26 is the GLC profile of the reaction product of Example XX(A)containing the isomers having the structures: ##STR31## wherein theratio of isomers is 1:2.2.

FIG. 27 is the GLC profile for the reaction product of Example XX(B)containing the compounds having the structures: ##STR32## wherein theratio of the isomers is 1:2.1.

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the reaction product of Example Icontaining the compound having the structure: ##STR33##

The peak indicated by the reference numeral "101" is for the compoundhaving the structure: ##STR34##

FIG. 5 is the GLC profile for the reaction product of Example II. Thepeak indicated on FIG. 5 by reference numeral "501" is the peak for thecompound having the structure: ##STR35##

FIG. 9 is the GLC profile for fraction 2 of the distillation product ofthe reaction product of Example III containing the compounds definedaccording to the structures: ##STR36##

The peaks indicated by reference numerals "901" and "902" are the peaksfor the isomers defined according to the structures: ##STR37## It isuncertain whether peak 901 or 902 is for the isomer having thestructure: ##STR38## and it is uncertain whether the peak 901 or 902 isfor the isomer having the structure: ##STR39##

FIG. 16 is the GLC profile for the reaction product of Example IVcontaining the compound having the structure: ##STR40## The peakindicated by reference numeral "162" on FIG. 16 is the peak for thereaction product having the structure: ##STR41## The peak indicated byreference numeral "161" on FIG. 16 is the peak for the starting materialfor the reaction, having the structure: ##STR42##

FIG. 20 is the GLC profile for the reaction product of Example Vcontaining the compound having the structure: ##STR43## The peakindicated by reference numeral "201" on FIG. 20 is the peak for thecompound defined according to the structure: ##STR44##

FIG. 24 is the GLC profile for the reaction product of Example VIcontaining the compound defined according to the structure: ##STR45##The peak indicated by reference numeral "241" on FIG. 24 is for thecompound defined according to the structure: ##STR46##

FIG. 25 is the GLC profile for the reaction product of Example XXcontaining the isomers having the structures: ##STR47## (conditions:SE-30 column operated isothermally at 210° C.). The ratio of isomers is1:3. The peak indicated by reference numeral "251" is the peak for thestarting material having the structure: ##STR48## The peak indicated byreference numeral "252" is for one of the isomers having the structures:##STR49## The peak indicated by reference numeral "253" is for one ofthe isomers: ##STR50##

FIG. 26 is the GLC profile for the reaction product of Example XX(A)(reaction operated at 30° C.). Conditions: SE-30 column operatedisothermally at 210° C. The ratio of product isomers having thestructures: ##STR51## is 1:2.2. The peak indicated by reference numeral"261" is the peak for the starting material having the sturcture:##STR52## The peak indicated by reference numeral "262" is for one ofthe isomers having the structures: ##STR53## The peak indicated byreference numeral "263" is for one of the isomers having the structure:##STR54##

FIG. 27 is the GLC profile for the reaction product of Example XX(B)(reaction operated at 55° C.). Conditions: SE-30 column operatedisothermally at 210° C. The ratio of isomers having the structures:##STR55## is 1:2.1. The peak indicated by reference numeral "272" is forone of the isomers having the structure: ##STR56## The peak indicated byreference numeral "273" is for one of the isomers having the structure:##STR57##

THE INVENTION

The present invention involves the use of1,2,3,3,5,6-hexamethyl-bicyclo[2.2.2]oct-5-en-2-ol in the form of anisomeric mixture or as individual isomers defined according to thestructures: ##STR58## as well as a process for preparing these isomers;and in addition, the perfume uses of these isomers and intermediatesuseful in carrying out the process for preparing these isomers.

The 1,2,3,3,5,6-hexamethyl-bicyclo[2.2.2]oct-5-en-2-ol producedaccording to the processes of our invention has fresh, strong,patchouli, ginger and camphoraceous aromas which are very long-lastingand extremely powerful. Even on dry-out the1,2,3,3,5,6-hexamethyl-bicyclo[2.2.2]oct-5-en-2-ol has excellent,aesthetically pleasing, strong, camphoraceous, patchouli notes. Incomparison to the products disclosed in U.S. Pat. Nos. 3,967,629,3,914,932 and 3,929,676, the1,2,3,3,5,6-hexamethyl-bicyclo[2.2.2]oct-5-en-2-ol of our invention hasa much more intense (3X) longer lasting (4X) than the nearestspecifically stated compound or isomer of the aforementioned patents. Inany event, the disclosures of the aforementioned patents, U.S. Pat. Nos.3,929,676, 3,914,932 and 3,967,629 are incorporated herein by reference.

The 1,2,3,3,5,6-hexamethyl-bicyclo[2.2.2]oct-5-en-2-ol of our inventioncan be prepared in two ways. The first manner of preparing the1,2,3,3,5,6-hexamethyl-bicyclo[2.2.2]-oct-5-en-2-ol of our invention isdisclosed in the aforementioned patents incorporated by reference hereinand involves the reaction of dimethyl acetylene having the structure:##STR59## with the compound having the structure: ##STR60## according tothe reaction: ##STR61## The resulting compound having the structure:##STR62## is then hydrogenated according to the reaction: ##STR63## toform the compound having the structure: ##STR64## This compound is thenreacted with an organometallic compound having the structure:

    CH.sub.3 M

in order to form a mixture of isomers defined according to thestructures: ##STR65## wherein M represents MgX or Li and X representschloro, bromo or iodo. This reaction is schematically illustrated asfollows: ##STR66## The resulting organometallic compounds definedaccording to the structures: ##STR67## are then treated with weak acidin order to form the mixture of isomers of our invention having thestructures: ##STR68##

The 1,2,3,3,5,6-hexamethyl-bicyclo[2.2.2]oct-5-en-2-ol of our inventioncan be prepared according to the novel process of our invention whichgives rise to higher conversions and higher yields and is, in general, amore efficient process than the above-mentioned process of the priorart. The novel process of our invention involves firstly, the reactionof the compound having the structure: ##STR69## with the compound havingthe structure: ##STR70## in accordance with the reaction: ##STR71##

The resulting compound defined according to the structure: ##STR72## isa novel compound. This compound may be hydrogenated stepwise to firstform the compound having the structure: ##STR73## which is then furtherhydrogenated catalytically to form the ketone defined according to thestructure: ##STR74## In the alternative, the compound having thestructure: ##STR75## may be hydrogenated with three moles of hydrogen inone step going through the intermediate: ##STR76## which is not isolatedto yield the compound having the structure: ##STR77##

Thereafter, the compound having the structure: ##STR78## is treated withthe compound:

    CH.sub.3 M

is the same manner as set forth supra to ultimately yield the isomers ofour invention having the structures: ##STR79##

The reaction of the compound having the structure: ##STR80## with thecompound having the structure: ##STR81## may be carried out in thepresence or in the absence of a reaction vehicle. Such a vehicle canfunction as a solvent for the reactions, to moderate the course of thereaction, to provide more intimate contact between the reactants and toimprove control over parameters such as temperature and pressure. Thereaction vehicle should be inert and is desirably one in which bothreactants are soluble. The reaction vehicle in this reaction may be anaromatic hydrocarbon such as benzene or a substituted aromatichydrocarbon particularly an alkyl substituted benzene such as toluene,xylene or the like.

The pressure under which the Diels-Alder reaction between the compoundhaving the structure: ##STR82## and the compound having the structure:##STR83## is carried out can vary over a range and is desirablysuperatmospheric. Pressures of from 150 to 400 psig are desirably used.

The Diels-Alder reaction can be carried out at temperatures of fromabout 150° C. up to about 300° C. Below the aforesaid lower temperature,the reaction proceeds at a very low rate.

On the other hand, at temperatures considerably higher than thosepreferred, the reaction may proceed uncontrollably and/or produce arelatively large quantity of unwanted by-products which lower the yieldof desirable materials and complicate purification of the product. Thepreferred temperature of the instant reaction between the compoundhaving the structure: ##STR84## and the compound having the structure:##STR85## is between 190° C. and 210° C. The resultant reaction producthaving the structure: ##STR86## can be purified and/or isolated byconventional methods as hereinafter mentioned.

The stepwise hydrogenation of the compound having the structure:##STR87## to form the intermediate having the structure: ##STR88## iscarried out with gaseous hydrogen. The hydrogenation is desirablycarried out at superatmospheric pressures of 150-600 psig and preferablyfrom 200 to 400 psig to provide a good reaction rate without substantialproduction of unwanted by-products.

The temperature is chosen so as to provide reaction times of about 1 to8 hours and preferably 2 to 6 hours. Accordingly, the temperaturesutilized are in the range of 20°-40° C., preferably from 25°-30° C.

The hydrogenation is desirably carried out in the presence of an inertvehicle, desirably a lower aliphatic alcohol. Preferred vehicles areethanol, propanol and isopropanol. The reaction is carried out in thepresence of a catalyst and the metallic hydrogenation catalyst such asnickel or precious metal such as platinum or palladium. The metalliccatalyst can be utilized on a carrier and a 5% palladium on carboncatalyst is utilized in certain preferred embodiments of our invention.

The intermediate having the structure: ##STR89## can be purified orisolated by conventional purification after appropriate washing,neutralizing or drying.

The intermediate having the structure: ##STR90## is further hydrogenatedto form the ketone having the structure: ##STR91## by means ofadditional hydrogenation at higher temperatures. The hydrogenation iscarried out with gaseous hydrogen and is desirably carried out atsuperatmospheric pressures of from 150-600 psig and preferably from200-400 psig to provide a good reaction rate without substantialproduction of unwanted by-products.

The temperature is chosen so as to provide reaction times of about 1 to8 hours and preferably 2 to 6 hours. Accordingly, the temperaturesutilized are in the range of 75° C. to 210° C. and preferably 75° C. to120° C.

The hydrogenation is desirably carried out in the presence of an inertvehicle, desirably a lower aliphatic alcohol. Preferred vehicles areethanol, propanol and isopropanol. The reaction is carried out in thepresence of a catalyst and the metallic hydrogenation catalyst such asnickel or precious metals such as platinum or palladium are desirable.The metallic catalyst can be utilized on a carrier and a 5% palladium oncarbon catalyst is utilized in certain preferred embodiments of ourinvention.

To obtain the 1,2,3,3,5,6-hexamethyl-bicyclo[2.2.2]oct-5-en-2olaccording to our invention, the ketone defined according to thestructure: ##STR92## is reacted with an organometallic compound havingthe structure:

    CH.sub.3 M

wherein m may be MgX or Li and X is chloro, bromo or iodo. Examples ofcompounds wherein M is MgX are methyl magnesium chloride, methylmagnesium bromide and methyl magnesium iodide. Examples where M is Li ismethyl lithium.

The reaction is preferably carried out in a vehicle. The vehicles arepolar organic solvents and solvents having a boiling point atatmospheric pressure in the range of 130°-140° C. are preferred. Thepreferred solvent is xylene. Surprisingly, using a xylene solvent at atemperature in the range of 135°-140° C. at atmospheric pressure, anoptimal ratio of isomers is obtained yielding optimal organoleptic(aroma) properties particularly concerning the aesthetic value of thelong lasting intense, patchouli aroma quality of the isomer mixture. Thereaction vehicle can also comprise phosphorous-containing materials suchas hexamethyl phosphoramide and the like.

The reaction vehicle as noted above can also include aromatic solvents,particularly monocyclic materials such as benzene, toluene and the like.

The reaction with the organometallic compound is desirably carried outat temperatures of from 10° C. to about 200° C. The use of temperaturessubstantially below this desirable range results in extremely lowreaction rates and the use of temperatures substantially above thisrange can result in undesirable by-products and unnecessarily highpressures. It is, accordingly, preferred to use temperatures in therange of from 80° C. to 150° C. and preferably from 130°-140° C.

The reaction can be carried out under a wide range of pressuresdepending on temperature and vehicles used but the atmospheric andsuperatmospheric pressures are preferred.

The quantity of compound having the structure:

    CH.sub.3 M

reacted with compound having the structure: ##STR93## can be varied overa wide range. It is desirable to use at least a stoichiometric quantityof organometallic compound, and quantities up to 250% of suchtheoretical amount can be utilized, that is, a 150% excess. In general,it is desirable to use from about 125% to about 200% of the theoreticalamount of organometallic compound to insure good reaction rates andcompleteness.

The time required for the reaction will vary depending upon thetemperature, pressure and the like. Ordinarily, reaction times of fromabout 2 to about 24 hours are desirable. It will be understood from thepresent disclosure, that temperatures of 100° C. will permit obtaininggood yields of organo-metalloid corresponding to the alcohol in fourhours with relatively small excesses of organometallic compounds whereaslonger times of 16 to 20 hours can be required with temperatures of 60°C. These organo-metalloids are defined according to the structures:##STR94## wherein M is defined as above.

After the reaction with the organometallic compound is completed to theextent desired, the product is then hydrolyzed by acidification orbasification to obtain the alcohols themselves having the structures:##STR95##

A base or an acid can be added to water and this can be used to wash andhydrolyze the salt, the product of the reaction. Such hydrolysis can becarried out over a wide range of temperatures from 5° C. to about 100°C. and temperatures of 15° C. to about 30° C. are preferred. In certainembodiments of the invention, the hydrolysis is carried out with anacidic medium such as saturated ammonium chloride solution.

As taught hereinafter, the isomers and mixtures of isomers of thepresent invention, the1,2,3,3,5,6-hexamethyl-bicyclo[2.2.2.]oct-5-en-2-ol of the presentinvention, has certain strong, patchouli, ginger and camphoraceous aromanuances which suit them for altering the aroma of consumable materialssuch as perfume compositions, colognes and perfumed articles, e.g. solidor liquid anionic, cationic, nonionic or zwitterionic detergents orfabric softener compositions or fabric softener articles, e.g. BOUNCE®manufactured by the Procter & Gamble Company of Cincinnati, Ohio.

According to our invention, a "perfume composition" is composed of asmall but effective amount of1,2,3,3,5,6-hexamethyl-bicyclo[2.2.2]oct-5-en-2-ol produced according tothis invention and an auxilliary perfume ingredient including, forexample, alcohols other than the1,2,3,3,5,6-hexamethyl-bicyclo[2.2.2]oct-5-en-2-ol isomers of ourinvention, aldehydes, ketones, nitriles, esters and frequentlyhydrocarbons which are admixed so that the combined odors of theindividual components produce a pleasant or desired fragrance. Suchperfume compositions usually contain (a) the main note or bouquet orfoundation stone of the composition; (b) modifiers which round off andaccompany the main notes; (c) fixatives which include odorous substanceswhich lend a particular note to the perfume throughout all stages ofevaporation and substances which retard evaporation and (d) topnoteswhich are usually low-boiling, fresh-smelling materials.

In perfume compositions, the individual component will contribute itsparticular olfactory characteristics but the overall effect of theperfume composition will be the sum of the effect of each ingredient.Thus, the 1,2,3,3,5,6-hexamethyl-bicyclo[2.2.2]oct-5-en-2-ol of thisinvention taken as individual isomers having the structures: ##STR96##or mixtures of these isomers in various proportions can be used to alterthe aroma characteristics of a perfume composition, for example, byhighlighting or moderating the olfactory reaction contributed by anotheringredient in the composition.

The amount of the 1,2,3,3,5,6-hexamethyl-bicyclo[2.2.2]oct-5-en-2-ol ofour invention either in admixture or as individual isomers which will beeffective in perfume compositions depends on many factors including theother ingredients, their amounts and the effects which are desired. Ithas been found that perfume compositions containing as little as 0.02%of the 1,2,3,3,5,6-hexamethyl-bicyclo[2.2.2]oct-5-en-2-ol of ourinvention, or even less, can be used to impart a scent odor to soaps,cosmetics, solid or liquid anionic, cationic, nonionic or zwitterionicdetergents, perfumed polymers, fabric softener compositions anddrier-added fabric softener articles such as BOUNCE® and other products.The amount employed can range up to 5% or higher of the fragrancecomponents and will depend on considerations of cost, nature of the endproduct, the effect desired on the finished product and the particularfragrance sought.

The 1,2,3,3,5,6-hexamethyl-bicyclo[2.2.2]oct-5-en-2-ol of our inventioneither taken as isomeric mixtures or considered as individual isomershaving the structures: ##STR97## can be used alone or in a perfumecomposition as an olfactory composition for augmenting, enhancing ormodifying the aromas of solid or liquid aionic, cationic, nonionic orzwitterionic detergents and soaps; space odorants and deodorants;perfumes; colognes; toilet waters; bath preparations such as bath oilsand bath salts; hair preparations such as lacquers, brilliantines,pomades and shampoos; cosmetic preparations such as creams, deodorants,hand lotions and sun screens; powders such as talcs, dusting powders,face powders and the like. When used as an olfactory component of aperfumed article, as little as 50 ppm of the1,2,3,3,5,6-hexamethyl-bicyclo[2.2.2]oct-5-en-2-ol of our invention willsuffice to impart a strong, camphoraceous, patchouli and ginger aromacharacter. Generally, no more than 5% of the perfumed article isrequired. Thus the range of1,2,3,3,5,6-hexamethyl-bicyclo[2.2.2]oct-5-en-2-ol in a perfumed articlevaries from 50 ppm up to 5% by weight.

All parts, percentages, proportions and ratios herein given are byweight unless otherwise indicated.

In addition, the perfume composition or fragrance composition cancontain a vehicle or carrier for the1,2,3,3,5,6-hexamethyl-bicyclo[2.2.2]oct-5-en-2-ol alone or takentogether with other ingredients. The vehicle can be a liquid such as analcohol, a glycol or the like. Examples of glycols are propylene glycol.Examples of alcohols are non-toxic alcohols such as ethyl alcohol. Thecarrier can be an absorbent solid such as a gum or components forencapsulating the composition such as by coacervation using gelatin orsuch as by forming a polymer wall around a liquid center as by using aurea formaldehyde prepolymer.

The following examples are given to illustrate embodiments of theinvention as it is presently preferred to practice it. It will beunderstood that these examples are illustrative and the invention is notto be considered as restricted thereto except as indicated in theappended claims.

EXAMPLE I PREPARATION OF1,3,3,5,6-PENTAMETHYL-BICYCLO[2.2.2]OCTA-5,7-DIEN-2-ONE

Reaction: ##STR98##

Into a 450 ml Parr mini-pressure reactor is placed 25 grams of2,6,6-trimethylcyclohexa-2,4-dien-1-one dimer, 75 ml of toluene and 12.4grams of 2-butyne.

The Parr reactor is sealed, flushed with nitrogen and heated to 180° C.After two hours at 180° C., GLC analysis indicates mostly startingmaterial and the temperature is raised to 200° C. After twelve hours at200° C., the reaction is approximately 70% complete. The reactionpressure at 200° C. is in the range of 120-150 psig.

The reaction mass is cooled and after cooling, an additional 2.4 gramsof 2-butyne is added. The reaction mixture is then heated at 200° C. foran additional 14 hours at 120-150 psig. The reaction mass is then cooledto room temperature and the toluene is removed in vacuo to yield 29.9grams of crude material.

A Rushover distillation gives 9.9 grams of1,3,3,5,6-pentamethyl-bicyclo[2.2.2]octa-5,7-dien-2-one boiling at55°-62° C. at 0.1 mm/Hg pressure. GLC analysis shows the material to be93% pure. Pure samples obtained by preparative GLC have the followingphysical properties:

IR spectrum (thin film): 3050 cm⁻¹, 2975, 2935, 2862, 1725, 1440, 1378,1009.

Mass spectrum: molecular ion at 190 m/e; then in descending order, 105,120, 70, 42.

Actual distillation fractions are as follows:

    ______________________________________                                        Vapor          Liquid                                                         Temp.          Temp.   Pressure                                               (°C.)   (°C.)                                                                          mm/Hg.                                                 ______________________________________                                        47              77     0.1                                                    55             105     0.1                                                    62             120     0.1                                                    56             133     0.1                                                    45             149     0.1                                                    ______________________________________                                    

FIG. 1 is the GLC profile for the reaction mass prior to distillation.Conditions: SE-30 column programmed from 120° C. to 210° C. at 8° C. perminute. The peak indicated by reference numeral "101" is the peak forthe ketone defined according to the structure: ##STR99##

FIG. 2 is the mass spectrum for the compound having the structure:##STR100##

FIG. 3 is the infra-red spectrum for the compound having the structure:##STR101## of peak 101 of FIG. 1.

FIG. 4 is the NMR spectrum for the compound of peak 101 of FIG. 1 havingthe structure: ##STR102## (Solvent CFCl₃ ; Field Strength 100 MHz).

EXAMPLE II PREPARATION OF1,3,3,5,6-PENTAMETHYL-BICYCLO[2.2.2]OCTA-5-EN-2-ONE

Reaction: ##STR103##

A solution of 37 grams of1,3,3,5,6-pentamethyl-bicyclo[2.2.2]octa-5,7-dien-2-one preparedaccording to Example I in 120 ml of isopropyl alcohol and 0.5 grams of10% palladium on carbon are placed in a hydrogenation apparatus andhydrogenated at 140-200 psig at a temperature in the range of 20°-35° C.

After a period of 69 minutes, the hydrogen uptake ceases and GLCanalysis indicates that all of the starting material has been consumed.After filtering to remove the catalyst, the isopropyl alcohol is removedat 25 mm/Hg pressure and the residue is distilled at reduced pressure(boiling point 55°-58° C. at 0.1 mm/Hg) in order to yield 27.5 grams ofproduct containing 92%1,3,3,5,6-pentamethyl-bicyclo[2.2.2]octa-5-en-2-one as analyzed by meansof GLC analysis.

Pure samples are obtained by preparative GLC.

The first distillation is carried out using a Vigreux equipped withfraction cutter yielding the following fractions:

    ______________________________________                                               Vapor    Liquid          Weight of                                     Fraction                                                                             Temp.    Temp.    Pressure                                                                             Fraction                                                                              %                                     Number (°C.)                                                                           (°C.)                                                                           mm/Hg  (grams) Product                               ______________________________________                                        1      47/65    93/91    4/2    0.8     14                                    2      56-60    89       0.6    0.4     44                                    3      65-74    93       2/2    0.8     53                                    4      70/71    91/91    1/1    1.3     81                                    5      55/56    91/91    0.25/0.3                                                                             1.7     90                                    6      56       92       0.1/0.3                                                                              3.2     93                                    7      58       92       0.25/0.1                                                                             3.9     94                                    8      58       93       0.1    5.0     94                                    9      58       93       0.2    4.9     94                                    10     52       93       0.1    8.8     93                                    11     53       110      0.1    4.0     85                                    12     57       125      0.1    2.0     67                                    ______________________________________                                    

Fractions 5, 6, 7, 8, 9 and 10 are bulked to yield the 27.5 grams of 93%pure product.

FIG. 5 is the GLC profile for the reaction product of this examplesubsequent to solvent stripping but prior to distillation. The peakindicated by reference numeral "501" is the peak for the ketone havingthe structure: ##STR104##

FIG. 6 is the mass spectrum for the compound of peak 501 of FIG. 5;having the structure: ##STR105##

FIG. 7 is the NMR spectrum for the compound of peak 501 of FIG. 5 havingthe structure: ##STR106## (Solvent CFCl₃ ; Field Strength 100 MHz).

FIG. 8 is the infra-red spectrum for the compound of peak 501 of FIG. 5having the structure: ##STR107##

EXAMPLE III PREPARATION OF1,2,3,3,5,6-HEXAMETHYL-BICYCLO[2.2.2]OCT-5-EN-2-OL

Reactions: ##STR108##

To a solution of 3.0 grams (15.6 milimoles) of1,3,3,5,6-pentamethyl-bicyclo[2.2.2]oct-5-en-2-one prepared according toExample II in 5.5 ml of tetrahydrofuran under a nitrogen atmosphere isadded 7.8 ml of 3.0 molar methyl magnesium chloride in tetrahydrofuranover a 2 minute period.

The resulting mixture is then heated to 70° C. for a period of 5 hours.After cooling the reaction mass to room temperature, the reaction massis quenched with 60 ml of saturated ammonium chloride solution. Theresulting top oil layer is separated and the bottom aqueous layer isextracted with 25 ml of methylene chloride. The extract and oil layersare combined, washed with 20 ml saturated sodium chloride solution,dried with anhydrous sodium sulfate and concentrated in vacuo to yield3.0 grams of crude 1,2,3,3,5,6-hexamethyl-bicyclo[2.2.2]oct-5-en-2-ol, amixture of isomers having the structures: ##STR109##

Distillation of this material in a short path distillation apparatusyields 1.8 grams of a material boiling at 113° C. at 5.7 mm/Hg. GLCanalysis on a Carbowax 20M column, 1/4"×8' stainless steel columnprogrammed from 120°-220° C. at 8° C. per minute shows that the materialis a mixture of 2 compounds in a 1:7 ratio. The two components areisolated by preparative GLC on a Carbowax column and prove to be theisomeric forms of the product having the structures: ##STR110##

FIG. 9 is the GLC profile for fraction 2 of the aforedescribeddistillation. The peaks indicated by reference numerals "901" and "902"are the peaks for the compounds having the structures: ##STR111##

FIG. 10 is the mass spectrum for the compound of peak 901 of FIG. 9having the structure: ##STR112##

FIG. 11 is the infra-red spectrum for the compound of peak 901 of FIG. 9having the structure: ##STR113##

FIG. 12 is the NMR spectrum for the compound of peak 901 of FIG. 9having the structure: ##STR114## (Solvent CFCl₃ ; Field Strength 100MHz).

FIG. 13 is the mass spectrum for the peak indicated by reference numeral902 of FIG. 9 for the compound having the structure: ##STR115##

FIG. 14 is the infra-red spectrum for the compound of peak 902 of FIG. 9having the structure: ##STR116##

FIG. 15 is the NMR spectrum for the compound of peak 902 of FIG. 9having the structure: ##STR117##

EXAMPLE IV PREPARATION OF5,6-BIS(HYDROXYMETHYL)-1,3,3-TRIMETHYLBICYCLO[2.2.2]OCTA-5,7-DIEN-2-ONEDIACETATE

Reaction: ##STR118##

To a 450 ml Parr mini-pressure reactor is charged 30 grams of2,6,6-trimethylcyclohexa-2,4-dien-1-one dimer, 105 ml of toluene and46.8 grams of 2-butyne-1,4-dioldiacetate. The reactor is sealed, flushedwith nitrogen and heated to 190° C. at 75-95 psig. After 3.7 hours, thereaction temperature is raised to 205° C. for 0.5 hours. The reactionmixture is then cooled to room temperature, transferred to a roundbottom flask and the toluene is removed in vacuo to yield 77 grams ofcrude 5,6-bis(hydroxymethyl)-1,3,3-trimethylbicyclo-octa-5,7-dien-2-onediacetate.

A pure sample is isolated by preparative GLC (8'×1/4" 25% SE-30 column,isothermal at 210° C.).

FIG. 16 is the GLC profile for the reaction product prior todistillation. The peak indicated by reference numeral "162" is the peakfor the product of reaction defined according to the structure:##STR119## The peak indicated by reference numeral "161" is the peak forthe starting material having the structure: ##STR120##

FIG. 17 is the mass spectrum for the peak indicated by reference numeral"162" of FIG. 16 defined according to the structure: ##STR121##

FIG. 18 is the infra-red spectrum for the compound of the peak indicatedby reference numeral "162" of FIG. 16 having the structure: ##STR122##

FIG. 19 is the NMR spectrum for the compound of the peak indicated byreference numeral "162" of FIG. 16 having the structure: ##STR123##(Solvent: CFCl₃ ; Field Strength 100 MHz).

EXAMPLE V PREPARATION OF5,6-BIS(HYDROXYMETHYL)-1,3,3-TRIMETHYLBICYCLO[2.2.2]OCTA-5-EN-2-ONEDIACETATE

Reaction: ##STR124##

To a 450 ml Parr mini-pressure reactor is charged 15 grams of5,6-bis(hydroxymethyl)-1,3,3-trimethylbicyclo[2.2.2]octa-5-dien-2-onediacetate produced according to Example IV, 60 ml of isopropyl alcoholand 0.3 grams of 10% palladium-on-carbon.

The reactor is flushed with nitrogen and then with hydrogen. Hydrogen isthen charged to a pressure of 190 psig and stirring is initiated. A 50psi pressure drop occurs within three minutes as the temperature risesfrom 22° to 27° C. There is no additional pressure drop during the next3.3 hours, during which the reaction takes place at 140 psig and 22°-30°C.

The reaction mass is filtered and after filtering, the reaction mass isconcentrated in vacuo to yield 13.6 grams of crude5,6-bix(hydroxymethyl)-1,3,3,-trimethyl-bicyclo-[2.2.2]octa-5-en-2-onediacetate.

A pure sample is isolated by preparative GLC (8'×1/4" 25% SE-30 columnoperated isothermally at 210° C.).

FIG. 20 is the GLC profile for the reaction product of this example. Thepeak indicated by reference numeral "201" is the peak for the compoundhaving the structure: ##STR125##

FIG. 21 is the infra-red spectrum for the compound of peak 201 of FIG.20 having the structure: ##STR126##

FIG. 22 is the NMR spectrum for the compound of peak 201 of FIG. 20having the structure: ##STR127## (Solvent: CFCl₃ ; Field Strength 100MHz).

FIG. 23 is the mass spectrum for the compound of peak 201 of FIG. 20having the structure: ##STR128##

EXAMPLE VI ONE STEP PREPARATION OF1,3,3,5,6-PENTAMETHYL-BICYCLO[2.2.2]OCTA-5-EN-2-ONE

Reactions: ##STR129##

To a 450 ml Parr mini-pressure reactor is charged 15 grams of5,6-bis(hydroxymethyl)-1,3,3-trimethylbicyclo[2.2.2]-octa-5,7-dien-2-onediacetate produced according to Example IV, 60 ml of isopropyl alcoholand 0.3 grams of 10% palladium on charcoal. After flushing with nitrogenand hydrogen, the hydrogen is charged to a pressure of 195 psig whilemaintaining the reaction mass temperature at 22°-27° C. Within fourminutes, the pressure drops to 140 psig and holds steady for sixminutes. Hydrogen is again charged to 195 psig and the temperature isgradually raised to 80° C. At 80° C. the pressure begins to drop. Thetemperature is raised to 85° C. and maintained at 85° C. until thepressure holds constant at 102 psig (1.7 hours). After cooling to roomtemperature, the reaction mass is filtered and the toluene is removed invacuo to yield 10.1 grams of1,3,3,5,6-pentamethyl-bicyclo[2.2.2]octa-5-en-2-one. This material isidentical to that prepared from 2,6,6-trimethylcyclohexa-2,4-dien-1-oneand 2-butyne according to Examples I and II, supra.

FIG. 24 is the GLC profile for the reaction product of this example. Thepeak indicated by reference numeral "241" is the peak for the compoundhaving the structure: ##STR130##

EXAMPLE VII PERFUME COMPOSITION

A perfume composition is prepared by admixing the following ingredientsin the indicated proportions:

    ______________________________________                                        Ingredient              Amount (Grams)                                        ______________________________________                                            n-decyl aldehyde            1.0                                               n-dodecyl aldehyde          2.0                                               methyl nonyl acetaldehyde   0.5                                               linalool                    50.0                                              linalyl acetate             70.0                                              phenyl ethyl alcohol        100.0                                             Pettigrain SA               20.0                                              Bergamot oil                30.0                                              alpha methyl ionone         25.0                                              mixture of isomers of 1',2',3',4'                                                                         10.0                                              5',6',7',8'-octahydro-2',3',8',8'-                                            tetramethyl-2'-acetonaphthones                                                produced by the process of Example                                            II (prior to GLC separation) of                                               U.S. Pat. No. 3,911,018 issued                                                on October 7, 1975                                                            cyclized bicylclo C-12 material                                                                           5.0                                               produced according to the process                                             of Example IV of Canadian Patent                                              854,225 issuedOctober 20, 1970                                                iso bornyl cyclohexyl alcohol                                                                             10.0                                              benzyl acetate              25.0                                              2-n-heptyl cyclopentanone   5.0                                               hexahydro-2,5,5-trimethyl-2H--2,4-                                                                        12.5                                              a-methanonaphthalene-1(5H)-one                                                prepared according to Example VIII                                            of U.S. Pat. No. 4,285,349                                                ______________________________________                                    

    ______________________________________                                        Ingredient             Amount (grams)                                         ______________________________________                                         ##STR131##                                                                        ##STR132##                                                                                         ##STR133##                                                                         12.5                                           ______________________________________                                    

The foregoing blend is evaluated and found to have a high degree ofrichness and persistence in its novel patchouli, amber, camphoraceousand ginger-like character. It also has excellent unique leathery notesin addition to the patchouli, camphoraceous and ginger-like notescontributed by the mixture of isomers prepared according to Example III.

This base composition can be admixed with aqueous ethanol, chilled andfiltered to produce a finished cologne. The cologne so prepared has anamber aroma with strong patchouli-like, ginger-like, camphoraceous andleathery nuances. The base composition can also be used to scent soap orother toilet goods such as lotions, aerosols, sprays and the like.

EXAMPLE VIII PREPARATION OF A COSMETIC POWDER

A cosmetic powder is prepared by mixing in a ball mill, 100 grams oftalcum powder with 0.25 grams of one of the products listed below inTable I. The resulting material has an excellent perfume aroma as setforth in Table I below.

                  TABLE I                                                         ______________________________________                                        Description of Composition                                                                        Fragrance Characteristics                                 ______________________________________                                        Mixture of tricyclic alcohols                                                                     A strong patchouli-like,                                  produced according to Example III                                                                 camphoraceous, ginger-                                    defined according to the structures:                                                              like aroma.                                                ##STR134##                                                                     and                                                                          ##STR135##                                                                     Perfume composition of Example                                                                  A strong, ambery, leather                                 VI                  aroma with patchouli,                                                         ginger-like and camphor-                                                      aceous nuances.                                           ______________________________________                                    

EXAMPLE IX PERFUMED LIQUID DETERGENT

Concentrated liquid detergents with aromas as set forth in Table I ofExample VIII (which detergents are produced from the lysine salt ofn-dodecyl benzene sulfonic acid as more specifically described in U.S.Pat. No. 3,948,818 issued on Apr. 6, 1976, the disclosure of which isincorporated by reference herein) are prepared containing the substancesset forth in Table I of Example VIII supra. They are prepared by addingand homogeneously mixing the appropriate quantity of substance of TableI of Example VIII in the liquid detergent. The detergents all possessexcellent aromas as set forth in Table I of Example VIII.

EXAMPLE X PREPARATION OF COLOGNE AND HANDKERCHIEF PERFUME

Perfume substances as set forth in Table I of Example VIII areincorporated into colognes at concentrations of 1.5%, 2.0%, 2.5%, 3.0%,3.5%, 4.0% and 5.0% in 80%, 85%, 90% and 95% aqueous food grade ethanol;and into handkerchief perfumes at concentrations of 10%, 15%, 20%, 30%,40% and 50% (in 90% and 95% aqueous food grade ethanol). Distinct anddefinitive fragrance aromas as set forth in Table I of Example VIII areimparted to the cologne and to the handkerchief perfumes.

EXAMPLE XI PREPARATION OF SOAP COMPOSITION

One hundred grams of soap chips (obtained from IVORY® soap) (a trademarkof the Procter & Gamble Company of Cincinnati, Ohio) are mixed with twograms of the materials as set forth in Table I of Example VIII until asubstantially homogeneous composition is obtained. The resultingcomposition is melted at 180° C. for a period of four hours under 15atmospheres nitrogen pressure. The resulting melt is cooled and formedinto soap bars. Each of the soap bars has an aroma as set forth in TableI of Example VIII.

EXAMPLE XII PREPARATION OF LIQUID DETERGENTS

Concentrated liquid detergents with aromas as set forth in Table I ofExample VIII containing 0.2%, 0.5% and 1.2% of the substances set forthin Table I of Example VIII are prepared by adding the appropriatequantity of the indicated composition as set forth in Table I of ExampleVIII to a liquid detergent known as P-87. The aromas of the liquiddetergent increase with increasing concentration of the composition asset forth in Table I of Example VIII.

EXAMPLE XIII FABRIC SOFTENER ARTICLE

Utilizing the procedure of Example I at column 15 of U.S. Pat. No.3,632,396 (the disclosure of which is incorporated by reference herein),a non-woven cloth substrate useful as a drier-added fabric softeningarticle of manufacture is prepared wherein the substrate, the substratecoating and the outer coating and the perfuming material are as follows:

1. a water "dissolvable" paper ("Dissolvo Paper");

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and

3. an outer coating having the following formulation (m.p. about 150°F.):

57% C₂₀₋₂₂ HAPS

22% isopropyl alcohol

20% antistatic agent

1% of composition as set forth in Table I of Example VIII.

Fabric softening compositions prepared as set forth below having thearoma characteristics as set forth in Table I of Example VIIIessentially consist of a substrate having a weight of about 3 grams per100 square inches; a substrate coating of about 1.85 grams per 100square inches of substrate; and an outer coating of about 1.4 grams per100 square inches of substrate thereby providing a total aromatizedsubstrate and outer coating weight ratio of about 1:1 by weight of thesubstrate. The aromas as set forth in Table I of Example VIII areimparted in a pleasant manner to the head space in the drier onoperation thereof using the said drier added fabric softening non-wovenfabric.

EXAMPLE XIV SOLID DETERGENT

Granular detergent compositions prepared according to United KingdomPatent Specification No. 1,501,498 having the following formulae areprepared by spray-drying the following mixture:

    ______________________________________                                        Ingredient             Percent by Weight                                      ______________________________________                                            Sodium salt of ethoxylated                                                    fatty alcohol sulfate having                                                  an average of about 2.25   14.1                                               moles of ethylene oxide per                                                   mole of fatty alcohol (1)                                                     Sodium tallow alkyl sulfate                                                                              2.4                                                Sodium silicate solids ratio:                                                                            0.0                                                SiO.sub.2 /Na.sub.2 O = 2.0                                                   Sodium silicate solids ratio:                                                                            1.0                                                SiO.sub.2 /Na.sub.2 O = 3.2                                                   Sodium tripolyphosphate    24.0                                               Na.sub.12 (AlO.sub.2.SiO.sub.2).sub.12 .27H.sub.2 O                                                      18.0                                               Moisture                   10.0                                               Sodium sulfate             25.0                                               Minor ingredients including                                                   sodium toluene sulfonate,                                                     trisodium sulfosuccinate, dyes,                                                                          4.0                                                brighteners                                                                   Perfume substance as set forth in                                                                        1.5                                                Table I of Example VIII                                                   ______________________________________                                         (1) Fatty alcohol composition: 66% C.sub.14 ; 33% C.sub.16 ; 1% C.sub.18.     (2) Prepared as described in United Kingdom Patent 1,501,498; average         particle size diameter 2 microns.                                        

Laundry solutions containing the above detergent composition are used tolaunder fabrics. Each of the laundry compositions both prior to and onlaundering give rise to the aromas as set forth in Table 1 of ExampleVIII.

EXAMPLE XV PERFUMED LIQUID DETERGENT

Concentrated liquid detergents having aromas as set forth in Table 1 ofExample VIII are prepared containing 0.10%, 0.15%, 0.20%, 0.40% and0.80% of one of the materials set forth in Table I of Example VIII. Theyare prepared by adding and homogeneously mixing the appropriate quantityof perfume substance in liquid detergent. The liquid detergent is abuilder-free liquid detergent consisting of (a) 50% of a nonionicsurfactant having an HLB of 8.0 and a critical micelle concentration of0.007, weight percent at 25° C.; (b) an ionic surfactant which istriethanolamine citrate; and (c) one weight percent of diethanolamineprepared according to United Kingdom Patent Specification No. 1,491,603(the specification for which is incorporated herein by reference).

The detergents all possess fragrances as set forth in Table I of ExampleVIII, the intensity increasing with greater concentrations of fragrancematerial.

EXAMPLE XVI PREPARATION OF 1,2,3,3,5,6-HEXAMETHYLBICYCLO[2.2.2]OCT-5-EN-2-OL

Reactions: ##STR136##

Into a 5 liter, three-neck round bottom flask equipped with mechanicalstirrer, "Y" tube, thermometer, one-liter addition funnel equipped withnitrogen inlet, Claissen head, Friedrich's condenser, heating mantle and6" 24/40 Vigreux column is placed 2,115 ml of commercial xylenes(mixture of ortho, meta and para xylene) (distilled) and 383 grams(1.995 moles) of the ketone having the structure: ##STR137## preparedaccording to Example VI.

The reaction mixture is heated to the range of 118°-133° C. and over afive hour period, 800 ml of a three molar solution of methyl magnesiumchloride and tetrahydrofuran (2.4 moles of methyl magnesium chloride) isadded to the reaction mass while simultaneously distilling and replacingthe xylene from the reaction mixture and into the reaction mixture (inorder to remove low-boiling tetrahydrofuran and keep the temperature ofthe reaction at about 130°-135° C.). At the end of the five hour period,4,300 ml of xylene was distilled out, replaced by 3,700 ml xylene.

The reaction mass is then cooled on a water/ice bath and 1,000 mlsaturated aqueous ammonium chloride is added to the reaction mass over aperiod of one hour while maintaining the reaction mass temperature at25°-49° C.

2,250 ml of the reaction mass is transferred to a 5 liter separatoryfunnel and 1,000 ml water is added thereto. There now exists twosections of the reaction product; one in the five liter reaction flaskand the second in the five liter separatory funnel.

1,700 ml water is added to the substance in the five liter flaskfollowed by:

45 ml 6 normal HCl

500 ml water

30 ml concentrated HCl

20 ml concentrated HCl

50 ml saturated ammonium chloride.

To the substance in the five liter separatory funnel, 1,800 ml water isadded followed by:

25 ml 6 normal HCl

150 ml water

10 ml concentrated HCl

50 ml saturated aqueous ammonium chloride.

The organic layers are combined and placed in a five liter separatoryfunnel. 500 ml water is added and the organic layer is separated fromthe aqueous layer. All of the aqueous phases formed above are combinedand extracted with two 500 ml portions of xylene. The xylene extractsare combined with the organic layer and the combined organic layers arewashed twice with 1,000 ml water. The organic phase is then filteredthrough coarse filter paper and dried on anhydrous sodium sulfate andthen stripped of xylene. GLC of the crude alcohol indicates an isomerratio of 1:4.

The organic phase is then distilled yielding the following fractions:

    __________________________________________________________________________         Vapor                                                                              Liquid    %   %   Total %                                                                            Wt. of                                       Fraction                                                                           Temp.                                                                              Temp.                                                                              Pressure                                                                           Isomer                                                                            Isomer                                                                            Tricyclic                                                                          Fract.                                       Number                                                                             (°C.)                                                                       (°C.)                                                                       mm/Hg                                                                              1   2   Alcohol                                                                            (grams)                                      __________________________________________________________________________    1    100/110                                                                            115/116                                                                            8/8  16.5                                                                              63.5                                                                              80.0 10.4                                         2    111.0                                                                              117.0                                                                              8    17.7                                                                              76.8                                                                              94.5 14.8                                         3    111.0                                                                              117.0                                                                              8    17.9                                                                              78.8                                                                              96.7 21.0                                         4    111.5                                                                              117.5                                                                              8    20.2                                                                              77.9                                                                              97.9 36.6                                         5    112.0                                                                              118.5                                                                              8    16.7                                                                              81.6                                                                              98.3 54.2                                         6    113.0                                                                              121.0                                                                              8    19.5                                                                              77.6                                                                              97.1 83.0                                         7    113.5                                                                              126.5                                                                              8    19.2                                                                              77.0                                                                              96.2 68.6                                         8    115.5                                                                              143.5                                                                              8    18.3                                                                              75.6                                                                              93.9 40.6                                         9    117.0                                                                              152.0                                                                              8    18.0                                                                              72.6                                                                              90.6  6.4                                         10   110.0                                                                              164.0                                                                              1    17.2                                                                              65.9                                                                              83.1 13.9                                         __________________________________________________________________________

Fractions 6 and 7 are bulked for subsequent organoleptic utilization.

Bulked fractions 6 and 7 have a strong camphoraceous, patchouli, gingeraroma with intense, long-lasting, camphoraceous and patchouli nuances ondry-out.

GLC, NMR, IR and mass spectral analyses yield the information that theproduct is identical to the product produced according to Example III inthat it contains the isomers having the structures: ##STR138##

EXAMPLE XVII HONEY PERFUME BASE FORMULATION

The following honey perfume base formulation is prepared:

    ______________________________________                                        Ingredients              Parts by Weight                                      ______________________________________                                            1,2,3,5,6-hexamethyl-                                                         bicyclo[2.2.2]oct-5-ene-2-ol,                                                 bulked fractions 6 and 7     100                                              prepared according to                                                         Example XVI                                                                   Coumarin                     100                                              Benzyl benzoate              400                                              Phenylethylphenyl acetate    100                                              Phenylethyl alcohol          100                                              Dimethylbenzylcarbinyl acetate                                                                             180                                              Phenylacetaldehyde dimethyl acetal                                                                         55                                               Phenylacetaldehyde diisopropyl acetal                                                                      32                                               Methyl anthranilate          82                                               1,3,3,5-tetramethyl-7-cyano- 41                                               bicyclo-[2.2.2]-octane                                                    ______________________________________                                    

The 1,2,3,3,5,6-hexamethyl-bicyclo[2.2.2]oct-5-ene-2-ol preparedaccording to Example XVI, bulked fractions 6 and 7 add an intense,strong, camphoraceous, ginger-like, patchouli-like character sonecessary for this natural honey formulation to cause it to have anatural honey/patchouli character.

EXAMPLE XVIII

Scented polyethylene pellets having a pronounced patchouli aroma withcamphoraceous and ginger nuances are prepared as follows:

In accordance with Example III of U.S. Pat. No. 3,505,432, thespecification for which is incorporated by reference herein, 75 poundsof polyethylene having a melting point of about 220° F. are heated toabout 230° F. in a container of the kind illustrated in FIGS. 1 and 2 ofU.S. Pat. No. 3,505,432. 25 pounds of the1,2,3,3,5,6-hexamethyl-bicyclo[2.2.2]oct-5-en-2-ol prepared according toExample XVI, bulked fractions 6 and 7 are then quickly added to theliquefied polyethylene, the lid is put in place and the agitating meansare actuated. The temperature is maintained at about 225° F. and themixing is continued for about 5-15 minutes. The valve at the bottom ofthe container is then opened to allow flow of the molten polyethyleneenriched with the tricyclic alcohol-containing material to exit throughthe orifices at the bottom of the holding tank. The liquid fallingthrough the orifices solidifies almost instantaneously upon impact withthe moving, cooled conveyor. Solid polyethylene beads or pellets havinga pronounced patchouli aroma with ginger and camphoraceous undertonesare thus formed. Analysis demonstrates that the pellets contain about25% of the 1,2,3,3,5,6-hexamethyl-bicyclo[2.2.2]oct-5-en-2-ol so thatalmost no losses of the scenting substance occur. These pellets may becalled master pellets. 50 pounds of the patchouli scent-containingmaster pellets are then added to 1,000 pounds of unscented polyethylenepowder and the mass is heated to the liquid state. The liquid is moldedinto thin sheets of films. The thin sheets of films have a pronouncedpatchouli aroma with ginger/camphoraceous undertones.

EXAMPLE XIX

100 pounds of polypropylene are heated to about 300° F. 30 pounds of theperfume composition described in Example XVII are added to the liquifiedpolypropylene. This procedure is carried out in the apparatus shown inFIGS. 1 and 2 of U.S. Pat. No. 3,505,432. After mixing for about 8minutes, the valve at the bottom of the container is opened to allow theexit of the polypropylene-scented material mixture whereby solid pelletshaving a pronounced honey/patchouli aroma are formed on the conveyorbelt. The pellets thus obtained are then admixed with about 20 timestheir weight of unscented polypropylene and the mixture is heated andmolded into flat discs. The flat discs have a strong and pleasanthoney/patchouli aroma.

EXAMPLES XX, XX(A) AND XX(B) PREPARATION OF1,2,3,3,5,6-HEXAMETHYL-BICYCLO[2.2.2]OCT-5-EN-2-OL

Reactions (for Examples XX, XX(A) and XX(B): ##STR139##

To a solution of 1.8 grams of1,3,3,5,6-pentamethyl-bicyclo[2.2.2]-5-oct-5-en-2-one having thestructure: ##STR140## prepared according to Example VI, in 11 ml oftetrahydrofuran, maintained at -20° C. is added 9 ml of a 1.3 molarsolution of methyl lithium in diethylether.

After stirring the reaction mass at -20° C. for a 10 minute period, asample is taken and treated with saturated ammonium chloride. Theorganic oil is separated. GLC analysis of the oil (conditions: SE-30column operated isothermally at 210° C.) shows a 1:3 ratio of isomers.

FIG. 25 is the GLC profile for this reaction product. The peak indicatedby reference numeral "251" is the peak for the starting material havingthe structure: ##STR141## The peak indicated by reference numeral "252"is the peak for one of the isomers having the structure: ##STR142## Thepeak indicated by reference numeral "253" is for one of the isomershaving the structure: ##STR143##

EXAMPLE XX(A)

The foregoing reaction is repeated at +30° C. instead of -20° C. GLCanalysis of the oil (conditions: SE-30 column operated isothermally at210° C.) shows a 1:2.2 ratio of isomers.

FIG. 26 is the GLC profile for this reaction mixture. The peak indicatedby reference numeral "261" is the peak for the starting material havingthe structure: ##STR144## The peak indicated by reference numeral "262"is the peak for one of the isomers having the structure: ##STR145## Thepeak indicated by reference numeral "263" is for one of the startingmaterials having the structure: ##STR146##

EXAMPLE XX(B)

The procedure of Example XX is carried out at +55° C. instead of -20° C.GLC analysis of the oil (conditions: SE-30 column operated isothermallyat 210° C.) shows a 1:2.1 ratio of isomers. The peak indicated byreference numeral "272" is the peak for one of the isomers having thestructure: ##STR147## The peak indicated by reference numeral "273" isfor one of the isomers having the structure: ##STR148##

What is claimed is:
 1. A compound defined according to a structureselected from the group consisting of:wherein Z represents hydrogen, MgXor Li and X represents chloro, bromo or iodo.
 2. A compound definedaccording to claim 1 having a structure selected from the groupconsisting of: ##STR149##
 3. The compound of claim 1 having a structureselected from the group consisting of: ##STR150##
 4. The compound ofclaim 1 having a structure selected from the group consisting of:##STR151##